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Kinetika Kimia

Studi/kajian tentang laju reaksi


http:// fpmipa.upi.edu/kuliahonline

Pengertian Laju reaksi


Pengukuran Laju
Penentuan Hk. Laju
Pengaruh Temperatur pada Laju reaksi
Mechanisme Reaksi
Catalysis
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Catalysis & Catalysts


Facts and Figures about Catalysts
Life cycle on the earth
Catalysts (enzyme) participates most part of life cycle
e.g. forming, growing, decaying
Catalysis contributes great part in the processes of converting sun energy to various
other forms of energies
e.g. photosynthesis by plant CO2 + H2O=HC + O2
Catalysis plays a key role in maintaining our environment

Chemical Industry

ca. $2 bn annual sale of catalysts


ca. $200 bn annual sale of the chemicals that are related products
90% of chemical industry has catalysis-related processes
Catalysts contributes ca. 2% of total investment in a chemical process
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What is Catalysis
Catalysis
Catalysis is an action by catalyst which takes part in a chemical reaction process and
can alter the rate of reactions, and yet itself will return to its original form without
being consumed or destroyed at the end of the reactions
(This is one of many definitions)
Three key aspects of catalyst action
taking part in the reaction
it will change itself during the process by interacting with other reactant/product
molecules

altering the rates of reactions


in most cases the rates of reactions are increased by the action of catalysts; however, in
some situations the rates of undesired reactions are selectively suppressed

Returning to its original form


After reaction cycles a catalyst with exactly the same nature is reborn
In practice a catalyst has its lifespan - it deactivates gradually during use
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Action of Catalysts
Catalysis action - Reaction kinetics and mechanism
Catalyst action leads to the rate of a reaction to change.
This is realised by changing the course of reaction (compared to non-catalytic reaction)
Forming complex with reactants/products, controlling the rate of elementary steps
in the process. This is evidenced by the facts that
The reaction activation energy is altered
uncatalytic

The intermediates formed are different from


The rates of reactions are altered (both
desired and undesired ones)

Reactions proceed under less demanding conditions

catalytic

energy

those formed in non-catalytic reaction

reactant
produc
reaction processt

Allow reactions occur under a milder conditions, e.g. at lower temperatures for those heat
sensitive materials

Action of Catalysts
It is important to remember that the use of catalyst DOES NOT vary G & Keq
values of the reaction concerned, it merely change the PACE of the process
Whether a reaction can proceed or not and to what extent a reaction can proceed is
solely determined by the reaction thermodynamics, which is governed by the values
of G & Keq, NOT by the presence of catalysts.
In another word, the reaction thermodynamics provide the driving force for a rxn; the
presence of catalysts changes the way how driving force acts on that process.
e.g CH4(g) + CO2(g) = 2CO(g) + 2H2(g)

G373=151 kJ/mol (100 C)


G973 =-16 kJ/mol (700 C)

At 100C, G373=151 kJ/mol > 0. There is no thermodynamic driving force, the reaction
wont proceed with or without a catalyst
At 700C, G373= -16 kJ/mol < 0. The thermodynamic driving force is there. However,
simply putting CH4 and CO2 together in a reactor does not mean they will react. Without a
proper catalyst heating the mixture in reactor results no conversion of CH4 and CO2 at all.
When Pt/ZrO2 or Ni/Al2O3 is present in the reactor at the same temperature, equilibrium
conversion can be achieved (<100%).
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Types of Catalysts & Catalytic


Reactions
The types of catalysts
Classification based on the its physical state, a catalyst can be
gas
liquid
solid

Classification based on the substances from which a catalyst is made


Inorganic (gases, metals, metal oxides, inorganic acids, bases etc.)
Organic (organic acids, enzymes etc.)

Classification based on the ways catalysts work


Homogeneous - both catalyst and all reactants/products are in the same phase (gas or liq)
Heterogeneous - reaction system involves multi-phase (catalysts + reactants/products)

Classification based on the catalysts action

Acid-base catalysts
Enzymatic
Photocatalysis
Electrocatalysis, etc.
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Applications of Catalysis

Industrial applications
Almost all chemical industries have one or more steps employing catalysts
Petroleum, energy sector, fertiliser, pharmaceutical, fine chemicals

Advantages of catalytic processes


Achieving better process economics and productivity
Increase reaction rates - fast
Simplify the reaction steps - low investment cost
Carry out reaction under mild conditions (e.g. low T, P) - low energy consumption

Reducing wastes
Improving selectivity toward desired products - less raw materials required, less unwanted wastes
Replacing harmful/toxic materials with readily available ones

Producing certain products that may not be possible without catalysts


Having better control of process (safety, flexible etc.)
Encouraging application and advancement of new technologies and materials
And many more

Applications of Catalysis

Environmental applications
Pollution controls in combination with industrial processes
Pre-treatment - reduce the amount waste/change the composition of emissions
Post-treatments - once formed, reduce and convert emissions
Using alternative materials

Pollution reduction
gas - converting harmful gases to non-harmful ones
liquid - de-pollution, de-odder, de-colour etc
solid - landfill, factory wastes

And many more

Other applications
Catalysis and catalysts play one of the key roles in new technology development.

Research in Catalysis
Research in catalysis involve a multi-discipline approach
Reaction kinetics and mechanism
Reaction paths, intermediate formation & action, interpretation of results obtained under
various conditions, generalising reaction types & schemes, predict catalyst performance

Catalyst development
Material synthesis, structure properties, catalyst stability, compatibility

Analysis techniques
Detection limits in terms of dimension of time & size and under extreme conditions (T, P)
and accuracy of measurements, microscopic techniques, sample preparation techniques

Reaction modelling
Elementary reactions and rates, quantum mechanics/chemistry, physical chemistry

Reactor modelling
Mathematical interpretation and representation, the numerical method, micro-kinetics,
structure and efficiency of heat and mass transfer in relation to reactor design

Catalytic process
Heat and mass transfers, energy balance and efficiency of process

Catalytic Reaction Processes


Understanding catalytic reaction processes
A catalytic reaction can be operated in a batch manner
Reactants and catalysts are loaded together in reactor and catalytic
reactions (homo- or heterogeneous) take place in pre-determined
temperature and pressure for a desired time / desired conversion
Type of reactor is usually simple, basic requirements
Withstand required temperature & pressure
Some stirring to encourage mass and heat transfers
Provide sufficient heating or cooling

Catalytic reactions are commonly operated in a continuous manner


Reactants, which are usually in gas or liquid phase, are fed to reactor in
steady rate (e.g. mol/h, kg/h, m3/h)
Usually a target conversion is set for the reaction, based on this target
required quantities of catalyst is added
required heating or cooling is provided
required reactor dimension and characteristics are designed accordingly.
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Catalytic Reaction Processes


Catalytic reactions in a continuous operation (contd)
Reactants in continuous operation are mostly in gas phase or liquid phase

easy transportation

The heat & mass transfer rates in gas phase is much faster than those in liquid

Catalysts are pre-loaded, when using a solid catalyst, or fed together with reactants
when catalyst & reactants are in the same phase and pre-mixed

It is common to use solid catalyst because of its easiness to separate catalyst from unreacted
reactants and products
Note: In a chemical process separation usually accounts for ~80% of cost. That
is why engineers always try to put a liquid catalyst on to a solid carrier.

With pre-loaded solid catalyst, there is no need to transport catalyst which is then more
economic and less attrition of solid catalyst (Catalysts do not change before and after a
reaction and can be used for number cycles, months or years),

In some cases catalysts has to be transported because of need of regeneration

In most cases, catalytic reactions are carried out with catalyst in a fixed-bed
reactor (fluidised-bed in case of regeneration being needed), with the reactant
being gases or liquids
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Catalytic
Reaction
Processes
General requirements for a good catalyst
Activity - being able to promote the rate of desired reactions
Selective - being to promote only the rate of desired reaction and also
retard the undesired reactions
Note: The selectivity is sometime considered to be more important
than the activity and sometime it is more difficult to achieve
(e.g. selective oxidation of NO to NO2 in the presence of SO2)
Stability -

a good catalyst should resist to deactivation, caused by

the presence of impurities in feed (e.g. lead in petrol poison TWC.

thermal deterioration, volatility and hydrolysis of active components

attrition due to mechanical movement or pressure shock

A solid catalyst should have reasonably large surface area needed for reaction
(active sites). This is usually achieved by making the solid into a porous
structure.
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Catalysis ; pengantar
Mekanisme umum:
Reaktan + katalis kompleks
Compleks Produk + Katalis
Klasifikasi Katalis
Katalis Homogen
Katalis Heterogen
Katalis Biologis (Enzyme)
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Katalis Homogen
Katalis homogen adalah zat yang berfasa sama dengan fasa
yang bereaksi yang ditambahkan untuk mempercepat suatu
reaksi
Contoh:
Katalis asam/basa, inisiatorH radikal, pelarut dsb.
C2 H 2 C6 H 6

CH 3CH 2

C2 H 2

CH 3CH 2 C6 H 6

C6 H 6

CH 3CH 2 C6 H 5

CH 3CH 2

CH 3CH 2 C6 H 6
CH 3CH 2 C6 H
5

H
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Katalis Heterogenous
H H
H H

Pt
surface
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Katalis Heterogenous
H H
H

H H

Pt
surface
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Heterogenous Catalysts
H H

Hydrogen bonds to surface of


metal.
Break H-H bonds
H

H H
H H

Pt
surface
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Heterogenous Catalysts

H
H H

Pt
surface
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Heterogenous Catalysts
The double bond breaks and bonds to the
catalyst.
H
H
H

H H

Pt
surface
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Heterogenous Catalysts
The hydrogen atoms bond with the carbon
H
H
H

H H

Pt
surface
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Heterogenous Catalysts

H
H

Pt
surface
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Heterogenous Catalysts
H H

Hydrogen bonds to surface of


metal.
Break H-H bonds
H

H H
H H

Pt
surface
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Heterogenous Catalysts

H
H H

Pt
surface
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Heterogenous Catalysts
The double bond breaks and bonds to the
catalyst.
H
H
H

H H

Pt
surface
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Heterogenous Catalysts
The hydrogen atoms bond with the carbon
H
H
H

H H

Pt
surface
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Heterogenous Catalysts

H
H

Pt
surface
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Kinetika Reaksi Katalitik


Kasus Khusus: Reaksi gas pada permukaan logam

Reaksi gas pada permukaan logam memiliki peranan


penting dalam berbagai proses:
Hidrogenasi
N 2 3H 2

Fe / K

C2 H 4 3 H 2

Ni

Keterangan:
Produksi pupuk dan as. nitrat

3 NH 3

Peningkatan Mutu minyak


bumi/angka oktane

C2 H 6

Dehidrogenasi
C2 H 4

Pt

C2H 2

Produksi Monomer

H2

Oksidasi
2CO 2 NO

C2 H 4

1
2

Pt / Rh

O2

Pt

2CO2
C2 H 4 O

N2

Katalitik Konverter
Produksi monomer

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Kinetika Reaksi Katalitik


Kasus Khusus: Reaksi gas pada permukaan logam

Reaksi fasa gas dg inisiator radikal (X)


X H 2 2H

X O2 2O X
O H 2 OH

H O2 OH O
X 2H H 2 X

Inisiasi

Propagasi

Terminasi

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Kinetika Reaksi Katalitik


Kasus Khusus: Reaksi gas pada permukaan logam

Mekanisme umum:
Adsorpsi
Adsorpsi
Disosiasi
Reaksi
Desorpsi produk
Disosiasi

katalis
Chemisorpsi

Physisorpsi

katalis

katalis
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Kinetika Reaksi Katalitik


Kasus Khusus: Reaksi gas pada permukaan logam

Adsorpsi

katalis

Chemisorpsi
Disosiasi

katalis

Mekanisme LangmuirHeinselwood

katalis
Reaksi
katalis
desorpsi

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Kinetika Reaksi Katalitik


Kasus Khusus: Reaksi gas pada permukaan logam

Adsorpsi
Chemisorpsi
Disosiasi

katalis
Mekanisme Eley Rideal
katalis

katalis
Reaksi
desorpsii

katalis

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Kinetika Reaksi Katalitik


Kasus Khusus: Reaksi gas pada permukaan logam
Langmuir Hinshelwood

Eley Rideal

N 2 6S 2 N ( ad )

N 2 6S 2 N ( ad )

H 2 2S 2 H ( ad )

N ( ad ) H 2 NH ( ad ) H ( ad )

N ( ad ) H ( ad ) NH ( ad ) 2S

NH ( ad ) H 2 NH 2 ( ad ) H ( ad )

NH ( ad ) H ( ad ) NH 2 ( ad ) 2S

NH 2( ad ) H 2 NH 3( ad ) H ( ad )

NH 2 ( ad ) H ( ad ) NH 3( ad ) 2S

2 H ( ad ) H 2

2S

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Kinetika Reaksi Katalitik


Kasus Khusus: Reaksi gas pada permukaan logam
rC k3 [ Aad ] k4 [Cad ]

Laju reaksi menjadi:


k3 K A PA S0 k4 K C PC S 0
r
1 K A PA K B PB K C PC

Jika k4 = 0:
Jika didefinisikan
A

[ Aads ]
S0

k3 K A PA S0
r
1 K A PA K B PB K C PC

K A PA
1 K A PA K B PB K C PC
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Kinetika Reaksi Katalitik


Kasus Khusus: Reaksi gas pada permukaan logam

Isotherm Langmuir,

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Katalisis pada proses Industri


Kasus Khusus: Katalis Asam (Zeolite)

Konsep bahwa padatan


dapat bersifat asam
muncul dari pengamatan
bahwa reaksi-reaksi
hidrocarbon dapat
dikatalisis dengan
andanya lempung asam
atau silica-alumina

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Katalisis pada proses Industri


Kasus Khusus: Katalis Asam (Zeolite)

Sifat Asam Katalis Padat

Zeolite merupakan
padatan silika-alumina
yang dapat berperan
sebagai katalis asam
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Katalisis pada proses Industri


Kasus Khusus: Katalis Asam (Zeolite)

Visualisasi Struktur Zeolith/Fauzaite

SEM image dari ZSM-5

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Katalisis pada proses Industri


Kasus Khusus: Katalis Asam (Zeolite)

Keistimewaan Material Zeolite:


- Memiliki struktur pori pada ukuran molekuler
(0.3 1 nm)
- Sebagai katalitik reaktor yang selektif

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